Adding Humic Acids to Gelatin Hydrogels: A Way to Tune Gelation

Exploring the chance to convert biowaste into a valuable resource, this study tests the potential role of humic acids (HA), a class of multifunctional compounds obtained by oxidative decomposition of biomass, as physical agents to improve gelatin’s mechanical and thermal properties. To this purpose, gelatin–HA aqueous samples were prepared at increasing HA content. HA/gelatin concentrations changed in the range 2.67–26.67 (wt/wt)%. Multiple techniques were employed to assess the influence of HA content on the gel properties and to unveil the underlying mechanisms. HAs increased gel strength up to a concentration of 13.33 (wt/wt)% and led to a weaker gel at higher concentrations. FT-IR and DSC results proved that HAs can establish noncovalent interactions through H-bonding with gelatin. Coagulation phenomena occur because of HA–gelatin interactions, and at concentrations greater than 13.33 (wt/wt)%, HAs established preferential bonds with water molecules, preventing them from coordinating with gelatin chains. These features were accompanied by a change in the secondary structure of gelatin, which lost the triple helix structure and exhibited an increase in the random coil conformation. Besides, higher HA weight content caused swelling phenomena due to HA water absorption, contributing to a weaker gel. The current findings may be useful to enable a better control of gelatin structures modified with composted biowaste, extending their exploitation for a large set of technological applications

Waste to Wealth Approach: Improved Antimicrobial Properties in Bioactive Hydrogels through Humic Substance–Gelatin Chemical Conjugation

Exploring opportunities for biowaste valorization, herein, humic substances (HS) were combined with gelatin, a hydrophilic biocompatible and bioavailable polymer, to obtain 3D hydrogels. Hybrid gels (Gel HS) were prepared at different HS contents, exploiting physical or chemical cross-linking, through 1-ethyl-(3-3-dimethylaminopropyl)carbodiimide (EDC) chemistry, between HS and gelatin. Physicochemical features were assessed through rheological measurements, X-ray diffraction, attenuated total reflectance (ATR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscopy (SEM). ATR and NMR spectroscopies suggested the formation of an amide bond between HS and Gel via EDC chemistry. In addition, antioxidant and antimicrobial features toward both Gram(−) and Gram(+) strains were evaluated. HS confers great antioxidant and widespread antibiotic performance to the whole gel. Furthermore, the chemical cross-linking affects the viscoelastic behavior, crystalline structures, water uptake, and functional performance and produces a marked improvement of biocide action

Enhanced Photoacoustic Response by Synergistic Ag–Melanin Interplay at the Core of Ternary Biocompatible Hybrid Silica-Based Nanoparticles

Photoacoustics (PA) is gaining increasing credit among biomolecular imaging methodologies by virtue of its poor invasiveness, deep penetration, high spatial resolution, and excellent endogenous contrast, without the use of any ionizing radiation. Recently, we disclosed the excellent PA response of a self-structured biocompatible nanoprobe, consisting of ternary hybrid nanoparticles with a silver core and a melanin component embedded into a silica matrix. Although preliminary evidence suggested a crucial role of the Ag sonophore and the melanin-containing nanoenvironment, whether and in what manner the PA response is controlled and affected by the self-structured hybrid nanosystems remained unclear. Because of their potential as multifunctional platforms for biomedical applications, a detailed investigation of the metal–polymer–matrix interplay underlying the PA response was undertaken to understand the physical and chemical factors determining the enhanced response and to optimize the architecture, composition, and performance of the nanoparticles for efficient imaging applications. Herein, we provide the evidence for a strong synergistic interaction between eumelanin and Ag which suggests an important role in the in situ-generated metal–organic interface. In particular, we show that a strict ratio between melanin and silver precursors and an accurate choice of metal nanoparticle dimension and the kind of metal are essential for achieving strong enhancements of the PA response. Systematic variation of the metal/melanin component is thus shown to offer the means of tuning the stability and intensity of the photoacoustic response for various biomedical and theranostic applications

Cyan Hydrogen Process: A New Route for Simultaneous Hydrogen Production and Carbon Valorization

Hydrogen is expected to largely contribute to the near-future circular economy. Today, most hydrogen is still produced from fossil fuels or renewable pathways with low efficiency and high cost. Herein, a proof of concept for a novel hydrogen production process is proposed, here named cyan hydrogen, inspired by a combination of the green and blue processes, due to the key role played by water and the low carbon content in the gas phase, respectively. The developed novel process, recently patented and demonstrated at the lab scale, is based on successive steps in which ethanol (5.0 mL) and water (10.0 mL) are alternately fed, with a fixed initial amount of sodium metaborate (2.0 g), in a batch reactor at 300 °C. Preliminary results showed the simultaneous production of a 95% v/v hydrogen stream, a polymeric byproduct with a repetitive carbon pattern −CH2–CH2–, and a liquid phase rich in oxygenated chemicals at temperatures lower than conventional hydrogen production processes

Detailed Thermal, Fire, and Mechanical Study of Silicon-Modified Epoxy Resin Containing Humic Acid and Other Additives

Following a waste-to-wealth approach, humic acid (HA) was exploited as a flame retardant additive. The effect of its addition alone and in combination with urea (UR) and ammonium polyphosphate (APP) on the thermal, fire, and mechanical performances of a bisphenol A diglycidyl ether (DGEBA)-based epoxy resin modified with (3-aminopropyl)-triethoxysilane (AP) and cured with aliphatic isophoronediamine (IDA) has been investigated. Unlike in previous studies, a UL 94-V-0 classification was achieved for epoxy resin containing HA at 6 wt % and APP at only 1 wt % phosphorus (P) loading. The presence of silicon-modified epoxy chains ameliorated the distribution of the biowaste within the resin, and the addition of HA alone avoided melt dripping. Besides, APP and UR promoted a remarkable reduction (up to 52%) of the peak heat release rate (pHRR) values and a significant delay (up to 21%) of the time to ignition in cone calorimetry tests, and hence an increase (up to 1.8 min) of the time to flashover, without any detrimental effect on the overall mechanical behavior. The evolved gas, thermal, and fire analysis was used to propose the combined mode of action of HA, UR, APP, and silicon in the fire performance improvement of the hybrid epoxy system